Field of the Invention
[0001] The present specification relates to articles having imagable coatings, for example
precursors for lithographic printing plates or for resist-coated electronic parts,
such as printed circuits. The invention relates further to methods of making and of
using such articles, and to novel compositions
per se.
Background of the Invention
[0002] A generally used type of lithographic printing plate precursor (by which we mean
a coated printing plate prior to exposure and development) has a radiation sensitive
coating applied to an aluminum substrate. A positive working precursor has a radiation
sensitive coating, which after imagewise exposure to radiation of a suitable wavelength
becomes more soluble in the exposed areas than in the non-exposed areas, in a developer.
Only the remaining, image, area of the coating is ink-receptive.
[0003] The differentiation between image and non-image areas is made in the exposure process
where a film is applied to the printing plate precursor with a vacuum to ensure good
contact. The printing plate precursor is then exposed to a radiation source; conventionally
this has been a UV radiation source. In the case where a positive printing plate precursor
is used, the area of the film that corresponds to the image in the printing plate
precursor is opaque so that no light will strike the printing plate precursor, whereas
the area on the film that corresponds to the non-image area is clear and permits the
transmission of light to the coating which becomes more soluble and is removed on
development.
[0004] In the manufacture of electronic parts such as printed circuits, after exposure to
radiation and development, the resist pattern is used as a mask for forming the patterns
onto the underlying electronic elements - for example by etching an underlying copper
foil. Due to the high resolution demands and the requirements of high resistance to
etching techniques, positive-working systems are widely used. In particular, in the
main there have been used alkali developable positive working resists mainly composed
of alkalisoluble novolac resins.
[0005] The types of electronic parts whose manufacture may use a resist include printed
wiring boards (PWBs), thick- and thin-film circuits, comprising passive elements such
as resistors, capacitors and inductors; multichip devices (MDCs); and integrated circuits
(ICs). These are all classified as printed circuits.
[0006] Imagable compositions may also be applied to plastics films in order to form masks.
The required pattern is formed on the mask, which is then used as a screen in a later
processing step, in forming a pattern on, for example, a printing plate or electronic
part precursor.
[0007] Common to virtually all commercial applications of positive working systems employing
UV radiation over several decades have been compositions comprising alkali soluble
phenolic resins and naphthoquinone diazide (NQD) derivatives. The NQD derivatives
have been simple NQD compounds used in admixture with resins, or NQD resin esters
in which the photoactive NQD moiety has been chemically attached to the resin itself,
for example by esterification of the resin with an NQD sulfonyl chloride.
[0008] US 3,802,885 describes a UV sensitive positive working printing plate containing
a naphthoquinone-(1,2)-diazide-(2)-5-sulphonic acid derivative, the printing life
of which is said to be improved by the inclusion of a polymeric carboxylic acid. Polymeric
carboxylic acids listed are cellulose acetate hydrogen phthalate, collophony-containing
resin, carboxyl group containing styrene-maleic acid copolymer, oil-free alkyd resin,
fatty acid-free phthalate resin and poly(vinyl hydrogen phthalate). Example 1 of US
3,802,885 describes a number of compositions each containing a polymeric carboxylic
acid, a novolac resin and 2,3,4-trihydroxy benzophenone tris-[naphthoquinone-(1,2)-diazide-(2)-5-sulphonate].
Each such composition was tested as a printing plate coating and found to have an
estimated life ("run length") of more than 200,000 copies. A comparison composition
without a polymeric carboxylic acid failed after 20 revolutions due to poor adhesion
of the image to the plate surface.
[0009] The naphthoquinone compounds of US 3,802,885 are known as 215-NQD compounds; the
moiety =O is at the 1-position, the moiety =N
2 is at the 2-position and the moiety -SO
2-X is at the 5-position (thus, on the adjacent fused ring of the naphthyl group).
[0010] Digital and laser imaging technology is now making new demands on coatings. We have
devised new positive working heat sensitive systems, to meet the new demands. In one
important development described in WO 99/01796 we determined that heat could image
coatings containing diazide moieties, without causing lysis of the diazide moieties.
Heat can be delivered to the coatings described in WO 99/01796 by conduction, using
a heated body such as a stylus, or by charged particle radiation, or, preferably,
by means of infra-red radiation, the coatings then containing suitable infra-red absorbers.
[0011] It would be desirable to increase the operating speed of imagable articles, but this
generally results in articles with lower chemical resistance - by which we mean resistance
to organic chemicals, notably those typically used in printing processes and in PCB
manufacture. Equally, it would be desirable to improve chemical resistance, but this
generally results in a reduction in operating speed. In practice a compromise must
be reached, and often the compromise is disappointing.
[0012] By "operating speed" in this specification we mean the criterion which is alternatively
known in the art as "sensitivity"; the question of how much energy is needed to effect
imaging, given also the developer conditions and other parameters selected. Thus,
when we mention "operating speed" in this specification we are considering this in
the context of the entire process of exposure and development. We are not referring
only to the matter of how the areas of the composition which are exposed react to
that exposure.
[0013] It is an object of embodiments of this invention to provide articles with imagable
coatings which have improved chemical resistance yet still with good operating speed;
or to provide articles with imagable coatings with improved operating speed, yet still
with good chemical resistance; or to provide articles with improved operating speed
and improved chemical resistance.
SUMMARY OF THE INVENTION
[0014] We have devised technology which offers improvement of our systems employing diazide
moieties, mentioned above, in both conventional photosensitive and thermal contexts,
such that their coatings continue to show good developability, with exposed areas
dissolving in aqueous developers and with unexposed areas remaining insoluble in such
developers, but wherein the coatings have good chemical resistance and good operating
speed.
[0015] To our surprise we have found that one particular class of polymeric carboxylic acids
are effective in achieving our objectives, in compositions containing diazide moieties.
[0016] In accordance with a first aspect of the invention there is provided a film-forming
composition comprising a carboxylic acid derivative of a cellulosic polymer, and a
diazide moiety, the composition having the property that when provided as a solid
coating on a substrate regions which have been exposed to imaging energy dissolve
in an aqueous developer and regions which have not been thus exposed are resistant
to dissolution in the aqueous developer and in organic liquid.
[0017] By "imaging energy" we mean radiation (electromagnetic or charged particle), or heat,
or both.
[0018] Preferably the remaining unexposed regions are more resistant to organic liquids
than the remaining unexposed regions of a corresponding coating treated in the same
way but not containing the carboxylic acid derivative of a cellulosic polymer.
[0019] We have found that the operating speed of the compositions of the invention is good.
Preferably the operating speed is higher than the operating speed of a corresponding
coating not containing the carboxylic acid derivative of a cellulosic polymer.
[0020] The composition may be a liquid composition, containing a solvent, or a solid composition,
for example a coating on a substrate, the solid composition being formed by the evaporation
of the solvent from the liquid composition. By "solid" we merely mean non-liquid.
[0021] In this specification weight percentages of components are expressed with reference
to a solid composition.
[0022] The presence of the carboxylic acid derivative of a cellulosic polymer appears to
confer upon the compositions improved resistance to certain organic liquids, for example
petroleum ethers, alkanediols, for example hexanediol, other glycols, glycol ethers,
straight-chain alkanols, for example ethanol, branched alkanols, for example isopropanol
and 1-methoxypropan-2-ol, cycloalkanols, for example cyclohexanol, and betaketoalkanols,
for example diacetone alcohol (ie 4-hydroxy-4-methyl-2-pentanone). When we refer herein
to a composition or coating as being resistant to organic liquids we are referring
to a composition or coating which is preferably resistant to organic liquids of at
least one of these classes (ie petroleum ethers; glycols and glycol ethers; and alkanols).
more preferably to organic liquids of at least two of them; and most preferably to
organic liquids of all three of them.
[0023] The composition may comprise a resin blend having as one resin component a carboxylic
acid derivative of a cellulosic polymer.
DETAILED DESCRIPTION OF THE INVENTION
[0024] Suitably the carboxylic acid derivative of a cellulosic polymer provides at least
0.25%, more preferably at least 0.5%, still more preferably at least 1%, yet more
preferably at least 2%, most preferably at least 5%, and, especially, at least 8%,
of the weight of the composition.
[0025] Suitably the carboxylic acid derivative of a cellulosic polymer provides up to 50%,
preferably up to 30%, more preferably up to 20%, still more preferably up to 16%,
and most preferably up to 12%, of the weight of the composition.
[0026] Preferably the acid number of the carboxylic acid derivative of the cellulosic polymer
is at least 50, more preferably at least 80, most preferably at least 100.
[0027] Preferably the acid number of the carboxylic acid derivative of the cellulosic polymer
does not exceed 210, and preferably does not exceed 180.
[0028] "Acid number" is the number of milligrams of potassium hydroxide needed to neutralize
1 gram of the acidic compound.
[0029] Said carboxylic acid derivative of a cellulosic polymer may be a carboxylic acid
derivative of a cellulose alkanoate, especially of a cellulose acetate.
[0030] The carboxylic acid derivatives of a cellulosic polymer may be reaction products
of cellulosic polymers and of carboxylic acids or, especially, of acid anhydrides
thereof. The carboxylic acids and acid anhydrides may be defined by the formulae
Y is suitably of the formula
[0031] where n represents an integer from 1 to 6, R
1 independently represents a hydrogen atom or an alkyl group (and when n is greater
than 1 the groups R
1 need not be identical with each other), R
2 represents a hydrogen atom or an alkyl group (and when is greater than 1 the groups
R
2 need not be identical with each other), R
5 represents a hydrogen atom or an alkyl group, R
6 represents a hydrogen atom or an alkyl group, or R
5 and R
6 together represent a chain such that the group -CR
5=CR
6- is an optionally substituted aryl or heteroaryl group.
[0032] Any alkyl group is suitably a C
1-6 alkyl group, preferably a C
1-4 alkyl group, and, most preferably, a methyl group.
[0033] An optionally substituted aryl group may be an optionally substituted naphthyl or,
especially, an optionally substituted phenyl group (such that the relevant anhydride
is phthalic anhydride).
[0034] An optionally substituted heteroaryl group may suitably comprise 5 or 6 ring atoms
of which 1 or more, preferably 1 or 2, are hetero atoms selected from oxygen, sulphur
or nitrogen. Preferred heteroaryl groups have 1 oxygen atom; or 1 sulphur atom; or
1 or 2 nitrogen atoms.
[0035] Optional substituents of an aryl or heteroaryl group may suitably be selected from
halogen atoms, and from C
1-4 alkyl, C
1-4 haloalkyl, cyano, C
1-4 alkoxy and carboxylic acid groups. There may suitably be 1-3 substituents but preferred
aryl or heteroaryl groups are unsubstituted.
[0036] Most preferably Y is selected from the following groups:
wherein each of R
1, R
2, R
3, R
4, R
5 and R
6 independently represents a hydrogen atom or an alkyl group.
[0037] Particularly preferred carboxylic acid derivatives of a cellulosic polymer are the
materials commercially available under the names CAP (cellulose acetate phthalate),
CAHP (cellulose acetate hydrogen phthalate - CAS No 9004-38-0) and CAT (cellulose
acetate trimellitate - CAS No 52907-01-4). Cellulose acetate propionate (CAS No 9004-39-1)
and cellulose acetate butyrate (CAS No 9004-36-8) are also commercially available
and may be useful.
[0038] In the present invention there is a requirement that the cellulosic polymer has carboxylic
acid functionality but it may have further functional groups, for example hydroxyl
groups or alkoxy groups, or groups containing an amide functionality.
[0039] The diazide moieties used in this invention preferably comprise diazo groups =N
2 conjugated to carbonyl groups, preferably via an aromatic or heteroaromatic ring.
In such moieties a carbonyl group is preferably bonded to the aromatic or heteroaromatic
ring at an adjacent ring position to the diazo group. Preferred moieties are benzoquinone
diazide, more preferably o-benzoquinonediazide (BQD) moieties (often referred to as
o-quinonediazides) and naphthoquinone diazide, more preferably onaphthoquinonediazide
(NQD) moieties.
[0040] A BQD moiety may, for example, comprise a 1,4- or, preferably 1,2-benzoquinonediazide
moiety.
[0041] An NQD moiety may, for example, comprise a 1,4-, 2,1- or, most preferably, a 1,2-naphthoquinone
diazide moiety.
[0042] Generally, NQD moieties are preferred to BQD moieties in the practice of the invention.
[0043] Most preferred in the practice of the present invention is a 1,2-naphthoquinonediazide
moiety.
[0044] The invention requires the use of a composition comprising a diazide moiety. The
diazide may be present as a simple compound admixed into the composition or, as is
preferred, as a moiety which is covalently bonded as a functional group to a polymer
of the composition.
[0045] Preferred diazide compounds are sulfonyl compounds in which the group -S02- is bonded
to an aromatic ring, suitably to the 5- or, especially, to the 4-position of a naphthyl
ring. Its other chemical bond may be to a polymer chain - the functionalisation approach
- or may be to a ballast moiety such as a hydroxylbenzophenone group, especially 2,4-dihydroxyphenone
- the admixture approach.
[0046] Examples of preferred naphthoquinone diazide moieties which may be used in the photosensitive
composition are disclosed in a variety of publications such as US Pat. Nos. 2,766,118;
2,767,092; 2,772,972; 2,859,112; 2,907,665; 3,046,110; 3,046,111; 3,046,115; 3,046,118;
3,046,119; 3,046,120; 3,046,121; 3,046,122; 3,046,123; 3,061,430; 3,102,809; 3,105,465;
3,635,709; and 3,647,443. Among these, preferred are o-naphthoquinonediazido sulfonates
or o-naphthoquinonediazido carboxylates of aromatic hydroxyl compounds; o-naphthoquinone
diazido sulfonic acid amides or o-naphthoquinonediazido carboxylic acid amides of
aromatic amine compounds, for instance, esters of naphthoquinone-1,2-diazido sulfonic
acid with polyhydroxyphenyl; esters of naphthoquinone-1,2-diazido-4-sulfonic acid
or naphthoquinone-1,2-diazido-5-sulfonic acid with pyrogallol/acetone resins; esters
of naphthoquinone-1,2-diazidosulfonic acid with novolac-type phenol/formaldehyde resins
or novolac-type cresol/formaldehyde resins; amides of poly(p-aminostyrene) and naphthoquinone-1,2-diazido-4-sulfonic
acid or naphthoquinone-l,2-diazido-5-sulfonic acid; esters of poly(p-hydroxystyrene)
and naphthoquinone-l,2-diazido-4-sulfonic acid or naphthoquinone-l,2-diazido-5-sulfonic
acid; and amides of polymeric amines with naphthoquinone-l,2-diazido-4-sulfonic acid.
The term "ester" used herein also includes partial esters.
[0047] Preferred compositions contain naphthoquinone diazide moieties of the following structure:
where X is preferably a polymer; but could be a ballast moiety, for example a dihydroxybenzophenone
group.
[0048] To our surprise we have found in our experimental work to date that in compositions
containing 214-NQD moieties the improvements in operating speed and run length are
significantly more pronounced than the improvements achieved when 215-NQD moieties
are used (those lesser improvements nonetheless being tangible and useful).
[0049] Preferably the composition contains, as a further resin component, a polymer having
hydroxyl groups. Preferably the further resin component, or the further resin components
in total, is/are present in a greater amount by weight than said carboxylic acid derivative
of a cellulosic polymer, or of said carboxylic acid derivatives of cellulosic polymers
in total. Preferably the composition contains at least 40%, more preferably at least
50%, still more preferably at least 70%, and most preferably at least 80% of such
a further resin component, or of such further resin components in total, by weight
based on the total weight of the composition.
[0050] Particularly useful phenolic resins in this invention are condensation reaction products
between appropriate phenols, for example phenol itself, C-alkyl substituted phenols
(including cresols, xylenols, p-tert-butyl-phenol, p-phenylphenol and nonyl phenols),
diphenols e.g. bisphenol-A (2,2-bis(4-hydroxyphenyl)propane), and appropriate aldehydes,
for example formaldehyde, chloral, acetaldehyde and furfuraldehyde and/or ketones,
for example acetone. Dependent on the preparation route for the condensation a range
of phenolic materials with varying structures and properties can be formed. Particularly
useful in this invention are novolac resins, resole resins and novolac/resole resin
mixtures. Most preferred are novolac resins. The type of catalyst and the molar ratio
of the reactants used in the preparation of phenolic resins determines their molecular
structure and therefore the physical properties of the resin. An aldehyde: phenol
ratio between 0.5:1 and 1:1, preferably 0.5:1 to 0.8:1 and an acid catalyst is used
to prepare novolac resins.
[0051] Examples of suitable novolac resins have the following general structure
[0052] Other polymers suitable for inclusion in the composition, notably in admixture with
a phenolic, preferably novolac, resin and the carboxylic acid derivative of a cellulosic
polymer, include: a polymer or copolymer of styrene, a polymer or copolymer of hydroxystyrene,
notably of 4-hydroxystyrene or 3-methyl-4-hydroxystyrene, a polymer or copolymer of
an alkoxystyrene, notably of 4-methoxystyrene, a polymer or copolymer of acrylic acid,
a polymer or copolymer of methacrylic acid, a polymer or copolymer of acrylonitrile,
a polymer or copolymer of acrylamide, a polymer or copolymer of vinyl alcohol, an
acrylate polymer or copolymer, a polymer or copolymer of methacrylamide, a sulphonamido
or imido polymer or copolymer, a polymer or copolymer of maleiimide or of alkylmaleiimide
or of dialkylmaleiimide, a polymer or copolymer of maleic anhydride (including partially
hydrolysed forms), a hydroxycellulose or a carboxycellulose.
[0053] Compositions intended for thermal imaging preferably include a compound which absorbs
radiation in the wavelength range 600-1400nm and converts it to heat.
[0054] A large number of compounds, or combinations thereof, can be utilized as radiation
absorbing compounds in preferred embodiments of the present invention.
[0055] The radiation absorbing compound may usefully be a pigment, which is a black body
or broad band absorber. It may be carbon such as carbon black or graphite. It may
be a commercially available pigment such as Heliogen Green as supplied by BASF or
Nigrosine Base NG1 as supplied by NH Laboratories Inc or Milori Blue (C.I. Pigment
Blue 27) as supplied by Aldrich.
[0056] The radiation absorbing compound may usefully be an infra-red absorbing dye able
to absorb the radiation selected for imaging and convert it to heat.
[0057] Preferably the infra-red absorbing compound is one whose absorption spectrum is significant
at the wavelength output of the laser which is (in preferred embodiments) to be used
in the method of the present invention. Usefully it may be an organic pigment or dye
such as phthalocyanine pigment. Or it may be a dye or pigment of the squarylium, merocyanine,
cyanine, indolizine, pyrylium or metal dithioline classes.
[0058] Suitably the radiation absorbing compound, when present, constitutes at least 0.25%,
preferably at least 0.5%, more preferably at least 1%, most preferably at least 2%,
of the total weight of the coating. Suitably the radiation absorbing compound, when
present, constitutes up to 25%, preferably up to 20%, and most preferably up to 15%,
of the total weight of the coating. There may be more than one radiation absorbing
compound. References herein to the proportion of such compound(s) are to their total
content.
[0059] In certain compositions of the present invention intended for heat imaging, the heat
is believed to produce areas which have transient increased solubility in the developer.
After an interval such areas may partially or wholly revert to their original, non-imaged
level of solubility. Thus the mode of action of such coatings does not require heatinduced
lysis of the modifying means but, more likely, the break-up of a physicochemical complex,
which can re-form. Consequently, in such embodiments the precursor is contacted with
a developer within a time period of 20 hours or less of the exposure to imaging heat,
preferably within about 120 minutes of exposure, and most preferably within 5 minutes
of exposure.
[0060] Suitably the composition contains a developer resistance means as defined in WO 99/21725,
suitably a siloxane, preferably constituting 1-10wt% of the composition. Preferred
siloxanes are substituted by one or more optionally-substituted alkyl or phenyl groups,
and most preferably are phenylalkylsiloxanes and dialkylsiloxanes. Preferred siloxanes
have between 10 and 100 -Si(R
1)(R
2)O- repeat units. The siloxanes may be copolymerised with ethylene oxide and/or propylene
oxide. For further information on preferred siloxanes the definitions in WO 99/21725
may be recited.
[0061] The compositions of the invention may contain other ingredients such as stabilising
additives, inert colorants, and additional inert polymeric binders as are present
in many positive working coatings.
[0062] In accordance with a second aspect of the invention there is provided a positive
working lithographic printing plate precursor or electronic part precursor or mask
precursor having a coating on a substrate, the coating comprising a composition as
defined above.
[0063] Preferably the coating is laid down from a liquid form of the composition, from which
a solvent is removed by evaporation, to form the dried coating.
[0064] After provision of the coating on the precursor the precursor may be subjected, as
part of its manufacture, to a stabilizing heat treatment step. We favor carrying out
the heat treatment at a temperature of at least 40°C, preferably at least 45°C, most
preferably at least 50°C. As regards the upper limit, we favor using a temperature
not in excess of 90°C, preferably not in excess of 85°C, most preferably not in excess
of 60°C. In general, heat treatments in which the maximum temperature does not exceed
the glass transition temperature (Tg) of the composition (as measured by differential
scanning calorimetry (DSC) at a heating rate of 10°C/minute) are favored. Such heat
treatments are suitably carried out on a stack of precursors or on a precursor coil,
and so are efficient.
[0065] We favor carrying out such a heat treatment for at least 4 hours; and preferably
for at least 24 hours and most preferably for at least 48 hours.
[0066] Preferably such a heat treatment takes place under conditions which inhibit the removal
of water from the precursor, for example by wrapping the precursor (or preferably
a stack or coil thereof) in a water impermeable material and/or by using humidity
control. For further information on such heat treatments WO 99/21715 can be referred
to.
[0067] A substrate may comprise a metal layer. Preferred metals include aluminum, zinc,
copper and titanium.
[0068] A substrate in embodiments of the invention intended as printing plate precursors
may be arranged to be non-ink-accepting. Said substrate may have a hydrophilic surface
for use in conventional lithographic printing using a fount solution or it may have
an inkrepelling surface suitable for use in waterless printing.
[0069] For printing applications the substrate may be aluminum which has undergone the usual
graining, anodic, and post-anodic treatments well known in the lithographic art for
enabling a radiation sensitive composition to be coated thereon and for its surface
to function as a printing background. Another substrate which may be used in the present
invention in the context of lithography is a plastics material base or a treated paper
base as used in the photographic industry. A particularly useful plastics material
base is polyethylene terephthalate which has been subbed to render its surface hydrophilic.
Also a so-called coated paper which has been corona discharge treated can be used.
[0070] Preferred printing plates have a substrate which has a hydrophilic surface and an
oleophilic ink-accepting coating.
[0071] For electronic part applications the substrate may comprise a copper sheet, for example
a copper/plastics laminate. After imaging and development an etching agent may be
used to remove exposed metal regions, leaving, for example, a printed circuit.
[0072] For certain mask applications the substrate may be a plastics film.
[0073] Thus in preferred embodiments a positive working pattern may be obtained after patternwise
exposure and development of a precursor of the present invention. The developer solubility
of the coating after it has been imaged during patternwise exposure is greater than
the solubility of the corresponding unexposed coating. In preferred embodiments this
solubility differential is increased by means of additional components and/or by resin
modification, as described herein. Preferably such measures reduce the solubility
of the polymeric composition, prior to the patternwise exposure. On subsequent patternwise
exposure the exposed areas of the coating are rendered more soluble in the developer,
than the unexposed areas. Therefore on patternwise exposure there is a change in the
solubility differential of the unexposed coating and of the exposed coating. Thus
in the exposed areas the coating is dissolved, to form the pattern.
[0074] The developer is dependent on the nature of the coating, but is preferably an aqueous
developer. Common components of aqueous developers are surfactants, chelating agents
such as salts of ethylenediamine tetraacetic acid, organic solvents such as benzyl
alcohol and phenoxy ethanol, phosphates, and alkaline components such as inorganic
metasilicates, hydroxides and bicarbonates, and mixtures of the foregoing.
[0075] Suitably the polymeric material
per se used in the film-forming composition of the invention is inherently soluble in an
alkaline developer. Suitably it is rendered insoluble in an alkaline developer by
means of one or more insolubilizer(s). Preferably, in use, it is more soluble in an
alkaline developer that it is in neutral liquids, such as water. Certain useful compositions
are substantially insoluble in neutral liquids, such as water.
[0076] Preferably an aqueous developer is an alkaline developer containing one or more inorganic
or organic metasilicates.
[0077] In the specification when we state that a coating is developer soluble we mean that
it is soluble in a selected developer, to an extent useful in a practical development
process. When we state that a coating is developer insoluble we mean that it is not
soluble in the selected developer, to an extent useful in a practical development
process.
[0078] In accordance with a third aspect of the invention there is provided a method of
preparing a printing plate, mask or electronic part from a positive working printing
plate, mask or electronic part precursor, the printing plate, mask or electronic part
precursor comprising
(a) substrate; and
(b) a coating on the substrate, wherein the coating comprises a composition of the
first aspect of the invention, the method comprising the steps of,
(i) exposing portions of the coating to imaging energy; and
(ii) removing the exposed portions of the coating using a developer liquid.
[0079] The imaging of selected portions may be effected by heat. In such embodiments exposure
is preferably effected by the use of infra-red electromagnetic radiation, the coating
preferably containing a radiation absorbing compound as defined above, or a radiation
absorbing compound being provided as a separate layer. In preferred thermal methods
the electromagnetic radiation employed for exposure is of wavelength at least 650nm,
preferably at least 700nm, and more preferably at least 750nm. Most preferably it
is at least 800nm. Suitably the radiation is of wavelength not more than 1350nm, preferably
not more than 1300nm, more preferably not more than 1200nm, and most preferably not
more than 1150nm. The radiation may be delivered by a laser under digital control.
Examples of lasers which can be used to expose coatings suitable for the method of
the present invention include semiconductor diode lasers emitting at between 600nm
and 1400nm, especially between 700nm and 1200nm. One example is the Nd YAG laser which
emits at 1064nm and another is the diode laser used in the Creo Trendsetter thermal
image setter, which emits at 830nm, but any laser of sufficient imaging power and
whose radiation is absorbed by the coating to produce heat, can be used. Alternatively
charged particle radiation could be used to deliver heat. Alternatively heat could
be delivered directly, by a heated body applied to the coating or to the reverse face
of the substrate. In this case no radiation absorbing compound is needed.
[0080] Preferably, however, the imaging of selected areas is effected by ultra-violet radiation
preferably of wavelength in the range which is believed causes the photolysis of the
diazide compound. This is believed to lead to the solubility change by several related
mechanisms, including the generation of an acidic decomposition product, believed
to be an indene carboxylic acid. The wavelength of the ultra-violet radiation is preferably
in the range 200-475nm, preferably 300-450nm. It may be delivered by a mercury lamp,
as is conventional.
[0081] In accordance with a fourth aspect of the invention there is provided an article
bearing a pattern in a coating thereon, produced by the method of the third aspect.
The article may be a mask or an electronic part but is preferably a printing plate,
ready for printing. If wished such a printing plate may undergo a baking step after
its chemical development for increased run length but this is not needed for most
printing applications.
[0082] In accordance with a fifth aspect of the invention there is provided a film-forming
composition comprising a carboxylic acid derivative of a cellulosic polymer, and a
diazide moiety, the composition having the property that when provided as a solid
coating on a substrate regions which have been exposed to imaging energy dissolve
in an aqueous developer and regions which have not been thus exposed are resistant
to dissolution in the aqueous developer; wherein the composition when provided as
a coating on a substrate is more resistant to dissolution in an organic liquid than
a corresponding composition not containing a carboxylic acid derivative of a cellulosic
polymer.
[0083] In accordance with a sixth aspect of the invention there is provided a film-forming
composition comprising a carboxylic acid derivative of a cellulosic polymer, and a
diazide moiety, the composition having the property that when provided as a solid
coating on a substrate regions which have been exposed to imaging energy dissolve
in an aqueous developer and regions which have not been thus exposed are resistant
to dissolution in the aqueous developer; wherein the composition when provided as
a solid coating on a substrate has a higher operating speed than a corresponding composition
not containing a carboxylic acid derivative of a cellulosic polymer.
[0084] In accordance with a seventh aspect of the invention there is provided a method of
preparing a printing plate or electronic part or mask from a positive working printing
plate, electronic part or mask precursor, the printing plate, electronic part or mask
precursor comprising
(a) a substrate; and
(b) an imagable coating on the substrate, wherein the coating comprises a carboxylic
acid derivative of a cellulosic polymer, and a diazide moiety; the methods comprising
the steps of
(i) exposing the coating imagewise; and
(ii) removing the exposed portions of the coating using a developer liquid; wherein
the coating is more resistant to dissolution in an organic liquid than a corresponding
composition not containing a carboxylic acid derivative of a cellulosic polymer.
[0085] In accordance with an eighth aspect of the invention there is provided a method of
preparing a printing plate or electronic part or mask from a positive working printing
plate, electronic part or mask precursor, the printing plate, electronic part or mask
precursor comprising
a) a substrate; and
b) an imagable coating on the substrate, wherein the coating comprises a carboxylic
acid derivative of a cellulosic polymer, and a diazide moiety; the methods comprising
the steps of
i) exposing the coating imagewise; and
ii) removing the exposed portions of the coating using a developer liquid; wherein
the coating is more resistant to dissolution in an organic liquid than a corresponding
composition not containing a carboxylic acid derivative of a cellulosic polymer.
[0086] In accordance with a ninth aspect of the invention there is provided a film-forming
composition comprising a carboxylic acid derivative of a cellulosic polymer and a
moiety decomposable by ultraviolet radiation, the composition having the property
that when provided as a solid coating on a substrate regions which have been exposed
to imaging energy dissolve in an aqueous developer and regions which have not been
thus exposed are resistant to dissolution in the aqueous developer and in an organic
liquid.
[0087] In accordance with a tenth aspect of the invention there is provided a method of
preparing a printing plate or electronic part or mask from a positive working printing
plate, electronic part or mask precursor which comprises
(a) a substrate; and
(b) an imagable coating on the substrate, the coating comprising a carboxylic acid
derivative of a cellulosic polymer and a moiety decomposable by ultra-violet radiation;
the method comprising the steps of
(i) exposing the coating imagewise to ultra-violet radiation; and
(ii) removing the exposed portions of the coating using a developer liquid.
[0088] In accordance with an eleventh aspect of the invention there is provided a method
of preparing a printing plate or electronic part or mask from a positive working printing
plate, electronic part or mask precursor which comprises
(a) a substrate; and
(b) an imagable coating on the substrate, wherein the coating comprises a carboxylic
acid derivative of a cellulosic polymer, and a diazide moiety;
the method comprising the steps of
(i) exposing the coating imagewise; and
(ii) removing the exposed portions of the coating using a developer liquid; wherein
the coating is more resistant to dissolution in an organic liquid than a corresponding
composition not containing a carboxylic acid derivative of a cellulosic polymer.
[0089] In accordance with a twelfth aspect of the invention there is provided a method of
preparing a printing plate or electronic part or mask from a positive working printing
plate, electronic part or mask precursor which comprises
(a) a substrate; and
(b) an imagable coating on the substrate, the coating comprising a carboxylic acid
derivative of a cellulosic polymer and a moiety decomposable by ultra-violet radiation;
the method comprising the steps of
(i) exposing the coating imagewise to ultra-violet radiation; and
(ii) removing the exposed portions of the coating using a developer liquid; wherein
the composition when provided as a coating on a substrate is more resistant to dissolution
in an organic liquid than a corresponding composition not containing a carboxylic
acid derivative of a cellulosic polymer.
[0090] In accordance with a thirteenth aspect of the invention there is provided a method
of preparing a printing plate or electronic part or mask from a positive working printing
plate, electronic part or mask precursor which comprises
(a) a substrate; and
(b) an imagable coating on the substrate, the coating comprising a carboxylic acid
derivative of a cellulosic polymer and a moiety decomposable by ultra-violet radiation;
the method comprising the steps of
(i) exposing the coating imagewise to ultra-violet radiation; and
(ii) removing the exposed portions of the coating using a developer liquid; wherein
the composition when provided as a solid coating on a substrate has a higher operating
speed than a corresponding composition not containing a carboxylic acid derivative
of a cellulosic polymer. dissolution in an organic liquid than a corresponding composition
not containing a carboxylic acid derivative of a cellulosic polymer.
[0091] The content of WO 99/01796, mentioned above, is hereby incorporated by reference.
[0092] A said compound decomposable by ultra-violet radiation may suitably be a latent Bronsted
acid.
[0093] The term "latent Bronsted acid" refers to a precursor which forms a Bronsted acid
by decomposition. Examples of Bronsted acids which are suitable for this purpose are
trifluoromethane sulphonic acid and hexafluorophosphoric acid.
[0094] The present invention is applicable to the systems described in US 5,491,046, incorporated
herein by reference, whose heat sensitive compositions comprise latent Bronsted acids.
These are negative working and positive working; the latter being of most interest
in the context of the present invention.
[0095] Ionic latent Bronsted acids are suitable. Examples of these include onium salts,
in particular iodonium, bromonium, chloronium, oxysulfonium, sulfoxonium, telluronium,
sulfonium, phosphonium, selenonium, diazonium and arsonium salts. Specific examples
of particularly useful onium salts include: diphenyliodonium hexafluorophosphate,
triphenylsulfonium hexafluoroantimonate, phenylmethyl-ortho-cyanobenzylsulfonium trifluoromethane
sulfonate, and 2-methoxy-4-aminophenyl diazonium hexafluorophosphate.
[0096] Non-ionic latent Bronsted acids are also suitable. Examples of these include compounds
of the formula:
and
wherein X is Cl, Br, F, or CF
2SO
3 and R
3 is an aromatic group, an aliphatic group or a combination of aromatic and aliphatic
groups.
[0097] Useful ionic latent Bronsted acids include those represented by the formula:
[0098] When Y is iodine then R
6 and R
7 are electron lone pairs and R
4 and R
5 are aryl or substituted aryl groups. When Y is S or Se then R
7 is an electron lone pair and R
4, R
5 and R
6 can be an aryl group, a substituted aryl group, an aliphatic group or a substituted
aliphatic group. When Y is P or As, then R
7 can be an aryl group, a substituted aryl group, an aliphatic group or a substituted
aliphatic group. W can be BF
4, CF
3SO
3, SbF
6, CCl
3CO
2, ClO
4, AsF
6, PF
6, or any corresponding acid whose pH is less than three.
[0099] Any of the onium salts described in U.S. 4,708,925, incorporated herein by reference,
can be utilized as the latent Bronsted acid.
[0100] An additional class of useful latent Bronsted acids are the haloalkyl-substituted
s-triazines. The haloalkyl-substituted s-triazines are well known photolytic acid
generators. Use of these compounds for this purpose is described, for example, in
U.S. 3,779,778, incorporated herein by reference.
[0101] Useful compounds are also described in US 5,466,557, 5,372,915 and 5,372,907, related
to US 5,491,046 and likewise incorporated herein by reference. We also believe the
present invention to be applicable to the phenolic resin systems described in US 4,708,925,
comprising an onium salt.
[0102] The following examples more particularly serve to illustrate the present invention
described hereinabove.
Materials
[0103] The following materials are referred to in these examples:
LB744: Rutaphen LB744 cresylic novolac resin, from Bakelite, Germany, having the structure:
214 NW744: A 214-naphthoquinone diazide-resin ester, made using the procedure described
below.
215 NW744: A 215-naphthoquinone diazide-resin ester, made using the procedure described
below.
[0104] To prepare 214 NW744, LB744 (100g) was reacted with 214NQD chloride (18g) by the
process outlined hereinafter.
[0105] To prepare 215 NW744, LB744 (100g) was reacted with 215NQD chloride (18g) by the
process outlined hereinafter.
[0106] 214-NQD chloride and 215-NQD chloride are as drawn above, but wherein the moiety
X is chloro.
[0107] The resins were modified by simple reaction with the acid chloride, in the following
manner:
1. Dissolve 25.0g of the phenolic resin in 61.8g of 2-methoxyethanol.
2. Immerse in a 3-necked 500ml round bottomed flask in a water bath placed on a hot
plate stirrer. Attach a stirrer gland, stirring rod and a thermometer to the flask.
3. Place the resin solution into the flask and begin rapid stirring.
4. Slowly add 25.6g of distilled water dropwise keeping precipitation to a minimum.
5. Add sodium hydrogen carbonate (4.3g) to the flask. Not all of the solid will dissolve.
6. Slowly add the desired acid chloride with vigorous stirring.
7. Warm the reaction mixture and maintain it for 6 hours at 40°C with stirring.
8. After 6 hours, remove the flask from the water bath and allow to cool (about 30
minutes).
9. Prepare a dilute solution by adding 8.6g 1.18 s.g. hydrochloric acid to 354g of
distilled water.
10. Slowly precipitate the esterified resin dropwise into the dilute acid with stirring.
11. Filter and wash the precipitate by re-slurrying in distilled water at least three
times, if possible until the pH of the filtrate reaches 6.0. In practice, it may only
reach 5.5.
12. Dry the precipitate in a vacuum oven at 40°C.
- RP2:
- A 214-NQD novolac resin ester from P.C.A.S., Longjumeau, France
- PD-140A:
- A novolac resin from Borden Chemicals, Ohio, USA
- "Triazine":
- 2-(4-methylthiophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine
- DHBP:
- the prioduct DHBP 85%, a 215-naphthoquinone diazide, a simple ester with dihydroxybenzophenone,
from P.C.A.S.
- CAHP:
- Cellulose Acetate Hydrogen Phthalate, from Aldrich Chemical Company, Gillingham, UK.
- Ethyl violet:
- A dye from Aldrich Chemical Company, Gillingham, UK, having the structure
Substrate
[0108] A 0.3mm thickness sheet of aluminum that has been hydrochloric acid electrograined
and anodized and post-anodically treated with an aqueous solution of an inorganic
phosphate.
Coating formulations
[0109] The proportions of (resin + NQD) components are set to 100 wt% - resin wt% and NQD
wt% (if present) therefore total 100 wt%. The term "owr" means "on weight of (resin
+ NQD)". All percentages are expressed with reference to weight of dry film.
[0110] Formulation concentrations were selected to provide a dry film weight of approximately
1.7gm
-2.
[0111] All formulations were coated onto the substrate by means of a wire wound bar.
[0112] All coated plates were dried for 80 seconds at 130°C in a MATHIS LABDRYER oven (as
supplied by Werner Mathis AG, Switzerland).
Tests
[0113] Operating speed: Plates were imagewise exposed on a MONTAKOP NOVA ultra-violet lightframe
(as supplied by Siegfried Theimer Grafische Gerate GmbH, Birstein, Germany), having
a mercury halide diazo bulb, with a STOUFFER control step wedge (as supplied by Kodak
Polychrome Graphics) and then developed with GOLDSTAR Positive Developer (as supplied
by Kodak Polychrome Graphics) at 20°C for 1 minute. The number of light units to give
a clear 3 STOUFFER step were calculated.
Fount resistance
[0114] Plates were prepared with strips of exposed areas to 10, 20, 30, 40, 50, 60, 70,
80, 90 and 100% of the exposure required to show a clear 3 on the STOUFFER wedge when
processed as above. A strip of unexposed plate was also included. The plates were
then immersed in a fount solution at 25°C for 1 hour. The fount solution was prepared
by mixing 165g propan-2-ol with 44g COMBIFIX XL and diluting to 1000ml with water.
The plates were then rinsed with water, dried and TESA 4122 adhesive tape applied
to half of each strip. The tape was then removed in one sharp movement to remove loose
coating. The degree of attack was then observed and a visual assessment of the degree
of attack was made, compared with a reference plate.
[0115] COMBIFIX XL is a standard fount solution additive available from Horstmann-Steinberg
of Germany. It comprises surfactants and printers add it, and similar products, to
fount solutions in order to keep the substrate ink free, to soften the water and to
aid ink dispersion over the plate surface.
Example 1 (comparative)
[0116] The following solutions were prepared:
40% wt% solution of 214 NW744 in 1-methoxypropan-2-ol
8.86 wt% solution of ethyl violet in 1-methoxypropan-2-ol
[0117] These were combined and coated to give a coating with a dry film composition of 100
wt% 214 NW744 + 1.5% owr ethyl violet.
Example 2
[0118] A 5 wt% solution of CAHP in 1-methoxypropan-2-ol was prepared.
[0119] A coating was prepared using this solution mixed with those shown in Example 1 to
give a dry film weight of 100 wt% 214 NW744 + 1.5% owr ethyl violet + 5% owr CAHP.
Example 3 (comparative)
[0120] A 40 wt% solution of 215 NW744 in 1-methoxypropan-2-ol was prepared.
[0121] A coating was prepared as in Example 1 but substituting the 214 NW744 with 215 NW744.
Example 4
[0122] A coating was prepared as in Example 2 but substituting the 214 NW744 with 215 NW744.
Example 5 (comparative)
[0123] The following solutions were prepared:
[0124] A 20 wt% solution of DHBP in dimethylformamide.
[0125] A 30 wt% solution of LB744 in 1-methoxypropan-2-ol.
[0126] A coating was prepared using these solutions and the ethyl violet solution described
in Example 1 to give a dry film composition of 20 wt% DHBP + 80 wt% LB744 + 1.5% owr
ethyl violet.
Example 6
[0127] A coating was prepared using solutions described above to give a dry film composition
of 20 wt% DHBP + 80 wt% LB744 + 1.5% owr ethyl violet + 5% owr CAHP.
Results for Examples 1 to 6
[0128] The following results were obtained:
Example |
Operating speed - light units to yield clear 3 STOUFFER step |
Fount resistance - degree of attack |
1 |
283 |
No attack on unexposed and 10% exposed strips.
Severe attack on remaining exposed strips. |
2 |
228 |
No attack on unexposed, 10% and 20% exposed strips.
Slight attack on remaining exposed strips. |
3 |
322 |
No attack on unexposed and 10% exposed strip.
Severe attack on remaining exposed strips. |
4 |
228 |
No attack on unexposed and 10% exposed strips.
Slight attack on 20% and 30% exposed strips. Severe attack on remaining exposed strips |
5 |
228 |
No attack on unexposed and 10% exposed strips.
Severe attack on remaining exposed strips. |
6 |
128 |
No attack on unexposed and 10% exposed strips.
Slight attack on 20% exposed strip.
Significant attack on remaining exposed strips. |
Conclusions on Examples 1 to 6
[0129] In all examples containing CAHP (Examples 2, 4 and 6) the operating speed of the
plate is faster than the corresponding example without CAHP (Examples 1, 3 and 5),
whilst at least retaining fount resistance. In the cases of Examples 2 and 4, the
fount resistance is improved, very substantially in the case of Example 2. In none
of the examples was there any significant fount attack in unexposed areas. None of
the samples was subjected to significant ambient light levels. Based on the above
results and of our experience we would expect samples which had been subjected to
significant ambient light levels to undergo some fogging and to have reduced fount
resistance in non-imaged regions. The above results indicate that the presence of
the CAHP can be expected to counter this effect and facilitate handling of precursors,
prior to imaging.
Example 7 (comparative)
[0130] The following solutions were prepared:
40 wt% solution of RP2 in 1-methoxypropan-2-ol
40 wt% solution of PD-140A in 1-methoxypropan-2-ol
8.86 wt% solution of ethyl violet in 1-methoxypropan-2-ol
3 wt% solution of triazine in n-butyl acetate
[0131] These were combined and coated to give a coating with a dry film composition of:
25 wt% RP2
75 wt% PD-140A
0.75% owr triazine
1.5% owr ethyl violet
Example 8
[0132] A 5 wt% solution of CAHP in 1-methoxypropan-2-ol was prepared.
[0133] A coating was prepared by mixing this solution with those described in Example 7
to give a dry film composition of:
25 wt% RP2
75 wt% PD-140A
0.75% owr triazine
1.5% owr ethyl violet
2% owr CAHP
Example 9
[0134] A coating was prepared by mixing the CAHP solution of Example 8 with those described
in Example 7 to give a dry film composition of:
25 wt% RP2
75 wt% PD-140A
0.75% owr triazine
1.5% owr ethyl violet
5% owr CAHP
Example 10
[0135] A coating was prepared by mixing the CAHP solution of Example 8 with those described
in Example 7 to give a dry film composition of:
25 wt% RP2
75 wt% PD-140A
0.75% owr triazine
1.5% owr ethyl violet
10% owr CAHP
Example 11
[0136] A coating was prepared by mixing the CAHP solution of Example 8 with those described
in Example 7 to give a dry film composition of:
25 wt% RP2
75 wt% PD-140A
0.75% owr triazine
1.5% owr ethyl violet
15°% owr CAHP
Results for Examples 7 to 11
[0137]
Example |
Operating speed - light units to yield clear 3 STOUFFER step |
Fount resistance - degree of attack |
7 |
171 |
No attack on unexposed strip. Slight attack on 10% exposed strip. Severe attack on
remaining exposed strips. |
8 |
171 |
No attack on unexposed, 10% and 20% exposed strips. Some attack on remaining exposed
strips. |
9 |
150 |
No attack on unexposed, 10%, and 20% exposed strips. Some attack on remaining exposed
strips. |
10 |
135 |
No attack on unexposed, 10%, 20% and 30% exposed strips. Slight attack on remaining
exposed strips. |
11 |
121 |
No attack on unexposed, 10%, 20%, 30% and 40% exposed strips. Slight attack on remaining
exposed strips. |
Conclusions on Examples 7 to 11
[0138] The higher the CAHP content of the coating the faster the plate speed and the more
resistant the coating to attack by the fount solution. Even a small level of CAHP
has a significant effect on the fount resistance and improves as the level is increased.
In none of the examples was there any significant fount attack in unexposed areas.
None of the samples was subjected to significant ambient light levels. Based on the
above results and of our experience we would expect samples which had been subjected
to significant ambient light levels to undergo some fogging and to have reduced fount
resistance in non-imaged regions. The above results further indicate that the presence
of the CAHP can be expected to counter this effect and facilitate handling of precursors,
prior to imaging.
[0139] The following product names given above are or may be trade marks: LB744, DHBP 85%,
RP2, MONTAKOP NOVA, GOLDSTAR, STOUFFER, COMBIFIX XL, MATHIS LABDRYER, CAHP.
[0140] While the invention has been described in terms of the foregoing specific embodiments,
it will be apparent to those skilled in the art that various alterations and modifications
may be made to the described embodiments without departing from the scope of the invention,
which is limited only by the appended claims. The disclosed embodiments are provided
merely by way of example.